US6902608B2 - Dental material containing phosphonic acids - Google Patents
Dental material containing phosphonic acids Download PDFInfo
- Publication number
- US6902608B2 US6902608B2 US10/332,344 US33234403A US6902608B2 US 6902608 B2 US6902608 B2 US 6902608B2 US 33234403 A US33234403 A US 33234403A US 6902608 B2 US6902608 B2 US 6902608B2
- Authority
- US
- United States
- Prior art keywords
- dental material
- group
- ethyl
- methyl
- aryl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000005548 dental material Substances 0.000 title claims abstract description 31
- 150000003009 phosphonic acids Chemical class 0.000 title claims abstract description 15
- 239000002318 adhesion promoter Substances 0.000 claims abstract description 23
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 239000004721 Polyphenylene oxide Chemical group 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 8
- 229920000570 polyether Chemical group 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- -1 R7: H Chemical group 0.000 claims description 7
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 7
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000945 filler Substances 0.000 claims description 6
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 6
- 150000007513 acids Chemical class 0.000 claims description 5
- 239000004568 cement Substances 0.000 claims description 5
- 239000002521 compomer Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910003849 O-Si Inorganic materials 0.000 claims description 2
- 229910003872 O—Si Inorganic materials 0.000 claims description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 2
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical compound C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 239000003505 polymerization initiator Substances 0.000 claims 1
- 230000007062 hydrolysis Effects 0.000 abstract description 4
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 13
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 0 [7*]C(=C)*P(=O)(O)O Chemical compound [7*]C(=C)*P(=O)(O)O 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 210000004268 dentin Anatomy 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000004809 Teflon Substances 0.000 description 4
- 229920006362 Teflon® Polymers 0.000 description 4
- KJBLLFKNQIHZFC-UHFFFAOYSA-N [4-methyl-4-(2-methylprop-2-enoylamino)pentyl]phosphonic acid Chemical compound CC(=C)C(=O)NC(C)(C)CCCP(O)(O)=O KJBLLFKNQIHZFC-UHFFFAOYSA-N 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 3
- 239000011350 dental composite resin Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 3
- 235000011007 phosphoric acid Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 2
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 2
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 2
- UNXURIHDFUQNOC-UHFFFAOYSA-N 5-bromo-2-methylpent-2-ene Chemical compound CC(C)=CCCBr UNXURIHDFUQNOC-UHFFFAOYSA-N 0.000 description 2
- UBFOUQPCKDTLOY-DHZHZOJOSA-N C=C(C)C(=O)NCC(C)CC/C(C)=C/P(=O)(O)O Chemical compound C=C(C)C(=O)NCC(C)CC/C(C)=C/P(=O)(O)O UBFOUQPCKDTLOY-DHZHZOJOSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- WYWZRNAHINYAEF-UHFFFAOYSA-N Padimate O Chemical compound CCCCC(CC)COC(=O)C1=CC=C(N(C)C)C=C1 WYWZRNAHINYAEF-UHFFFAOYSA-N 0.000 description 2
- AMFGWXWBFGVCKG-UHFFFAOYSA-N Panavia opaque Chemical compound C1=CC(OCC(O)COC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OCC(O)COC(=O)C(C)=C)C=C1 AMFGWXWBFGVCKG-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229930006711 bornane-2,3-dione Natural products 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229950000688 phenothiazine Drugs 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- HSFXEOPJXMFQHG-ARJAWSKDSA-N (z)-4-[2-(2-methylprop-2-enoyloxy)ethoxy]-4-oxobut-2-enoic acid Chemical compound CC(=C)C(=O)OCCOC(=O)\C=C/C(O)=O HSFXEOPJXMFQHG-ARJAWSKDSA-N 0.000 description 1
- DSAYAFZWRDYBQY-UHFFFAOYSA-N 2,5-dimethylhexa-1,5-diene Chemical compound CC(=C)CCC(C)=C DSAYAFZWRDYBQY-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- HQHKCNMTLZRXIP-UHFFFAOYSA-N 4-[2-(2-methylprop-2-enoyloxy)ethoxycarbonyl]benzoic acid Chemical compound CC(=C)C(=O)OCCOC(=O)C1=CC=C(C(O)=O)C=C1 HQHKCNMTLZRXIP-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 241000283690 Bos taurus Species 0.000 description 1
- DTBCLFYCUGWADK-UHFFFAOYSA-N C=C(C)C(=O)NCCC[Si](C)(C)O[Si](C)(C)CCCP(=O)(O)O Chemical compound C=C(C)C(=O)NCCC[Si](C)(C)O[Si](C)(C)CCCP(=O)(O)O DTBCLFYCUGWADK-UHFFFAOYSA-N 0.000 description 1
- ZLICBLLSPCQFQJ-SOFGYWHQSA-N C=C(C)CC/C(C)=C/P(=O)(O)O Chemical compound C=C(C)CC/C(C)=C/P(=O)(O)O ZLICBLLSPCQFQJ-SOFGYWHQSA-N 0.000 description 1
- YGINTXGWMLCRPS-UHFFFAOYSA-N C=C(COCCN(CP(=O)(O)O)C[PH](=O)(=O)O)C(=O)OCC Chemical compound C=C(COCCN(CP(=O)(O)O)C[PH](=O)(=O)O)C(=O)OCC YGINTXGWMLCRPS-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 102100026735 Coagulation factor VIII Human genes 0.000 description 1
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 1
- 229910006124 SOCl2 Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- UBFOUQPCKDTLOY-UHFFFAOYSA-N [2,5-dimethyl-6-(2-methylprop-2-enoylamino)hex-1-enyl]phosphonic acid Chemical compound CC(=C)C(=O)NCC(C)CCC(C)=CP(O)(O)=O UBFOUQPCKDTLOY-UHFFFAOYSA-N 0.000 description 1
- OQHMGFSAURFQAF-UHFFFAOYSA-N [2-hydroxy-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)COC(=O)C(C)=C OQHMGFSAURFQAF-UHFFFAOYSA-N 0.000 description 1
- AMUNHMVMESMYQL-UHFFFAOYSA-N [2-hydroxy-3-[4-[2-[4-[2-hydroxy-3-(2-methylprop-2-enoyloxy)propyl]phenyl]propan-2-yl]phenyl]propyl] 2-methylprop-2-enoate Chemical compound C1=CC(CC(O)COC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(CC(O)COC(=O)C(C)=C)C=C1 AMUNHMVMESMYQL-UHFFFAOYSA-N 0.000 description 1
- XZRUDDFTZNELMF-UHFFFAOYSA-N [H]OP(=O)(CCC=C(C)C)O[H] Chemical compound [H]OP(=O)(CCC=C(C)C)O[H] XZRUDDFTZNELMF-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- IYYIVELXUANFED-UHFFFAOYSA-N bromo(trimethyl)silane Chemical compound C[Si](C)(C)Br IYYIVELXUANFED-UHFFFAOYSA-N 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- VDQQXEISLMTGAB-UHFFFAOYSA-N chloramine T Chemical compound [Na+].CC1=CC=C(S(=O)(=O)[N-]Cl)C=C1 VDQQXEISLMTGAB-UHFFFAOYSA-N 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- GTZOYNFRVVHLDZ-UHFFFAOYSA-N dodecane-1,1-diol Chemical compound CCCCCCCCCCCC(O)O GTZOYNFRVVHLDZ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000003178 glass ionomer cement Substances 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 210000004283 incisor Anatomy 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 210000000214 mouth Anatomy 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000005591 trimellitate group Chemical group 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3826—Acyclic unsaturated acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
- C07F9/3821—Acyclic saturated acids which can have further substituents on alkyl substituted by B, Si, P or a metal
Definitions
- the invention relates to dental materials, in particular adhesion promoters or polymerizable cements, for example compomers or glass ionomer cements with polymerizable acids, which are known in principle from DE-A-3536076 and DE-A-3536077.
- Dental materials with polymerizable phosphoric acids as comonomers are known; they usually comprise phosphoric acid and acrylates or methacrylates.
- DE-A-19647140 discloses the esterification of a hydroxyalkyl acrylate or methacrylate with phosphate.
- a disadvantage of these substances is that they have a low resistance to hydrolysis, since the ester bonds between phosphate and alkyl chain and between methacrylate and alkyl chain can be easily cleaved hydrolytically. This reduces the storage stability of the dental material and results, under the conditions in the oral cavity, in a reduced durability in the tooth.
- DE-A-19746708 discloses the bonding of phosphonates to the methyl group of a methacrylate ester via a spacer.
- Phosphine oxides linked to methacrylates or styrene via a urethane group are also known (J. Smid et al., Journal of Polymer Science, Part A Polymer Chemistry, 31, 239-247 (1993)), as is the linking of phosphonic acids to methacrylates via an ester (DE-A-19918974).
- the invention is based on the object of preparing dental materials of the kind mentioned at the start which have good adhesive properties and a high resistance to hydrolysis.
- the dental materials comprise phosphonic acids with the structure given below or salts of these acids: in which R, R 7 and p are, independently of one another: either:
- the invention is based on the surprising discovery that molecules with a relatively long chain bridge between phosphonic acid group and reactive double bond, as defined in the claim, have a high resistance to hydrolysis and, at the same time, improved adhesive properties.
- R 1 is hydrogen or an alkyl or aryl group.
- R 1 is chosen from the group consisting of hydrogen, methyl, ethyl and isopropyl.
- R 2 is an alkyl group with 4 to 18 C-atoms which can be straight or branched. Preferably, it comprises 6 to 12 C-atoms.
- R 2 can also have the form of an alkyl chain interrupted by ether groups or additional urethane groups.
- the phosphonic acids have the following structure:
- R 3 or R 4 are aryl or alkyl groups.
- the alkyl groups can be straight or branched and preferably have 3 to 12 C-atoms.
- the substituents R 5 are identical or different and are methyl, ethyl or phenyl groups.
- m is 1 to 10.
- diphosphonates can preferably be used in the dental materials according to the invention:
- X is nitrogen, boron or a CH group
- R 6 is a straight or branched alkyl group with at least 3 C-atoms, an aryl group or a polyether group with 1 to 10 polyether units
- Y comprises ethylenically unsaturated double bonds
- Y is in particular chosen from the group consisting of CH 2 ⁇ CH—O—, styrene, methacrylamide and CH 2 ⁇ C(COOR 12 )—CH 2 —, in which R 12 is H, methyl, ethyl, propyl, isopropyl or butyl.
- the invention also relates to the use of a dental material according to the invention as adhesion promoter, compomer or polymerizable cement.
- the dental material can consist exclusively of the phosphonic acids mentioned or of their salts; it can comprise one or more solvents and/or additional polymerizable monomers, such as, in particular, acrylates or methacrylates.
- Suitable solvents for dental materials are familiar to a person skilled in the art; water, methanol, ethanol, isopropanol, acetone, ethyl methyl ketone, ethyl acetate and mixtures of the aforementioned compounds are preferred.
- water-soluble methacrylates for example hydroxyethyl (meth)acrylates or hydroxypropyl (meth)acrylates
- (Meth)acrylates having at least two methacrylate groups for example ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, hexanediol di(meth)acrylate, butanediol di(meth)acrylate, dodecanediol di(meth)acrylate, 2,2-bis[p-(hydroxy(meth)acryloyloxy)-phenyl]propane, ethoxylated bisphenol A di(meth)acrylate, glycerol di(meth)acrylate, urethane di(meth)acrylate, polyester urethane di(meth)acrylate, trimethylolpropane tri(meth)acrylate or
- An additional acid in the form of a polymerizable carboxylic acid can also be added.
- Examples which may be mentioned are mono(2-methacryloyloxyethyl)maleate, mono(2-methacryloyloxyethyl)phthalate and mono(2-methacryloyloxyethyl)trimellitate.
- the term “dental materials” is understood to mean all materials which find application in the context of restorative or prosthetic work on teeth and which comprise phosphonates according to the invention or their salts.
- the phosphonic acids according to the invention can be used in adhesion promoters.
- Dental materials according to the invention can in particular have the following components:
- a proportion of 0-20% by weight of fillers is preferred for adhesion promoters; cements and compomers are preferably solvent-free and the proportion of filler is preferably between 40 and 80% by weight.
- the mixture is diluted with 100 ml of dichloromethane, and 300 ml of a 5M NaOH solution are added dropwise with cooling and vigorous stirring. After 2 h, the reaction mixture is diluted with 300 ml of water, and 300 ml of 25% phosphoric acid are added with cooling.
- the preparation is cooled down and is then dissolved in a mixture of 1.16 ml of water and 10 ml of methanol, and the sulfuric acid is neutralized through addition of a solution of 1.46 g of NaOH, 1.1 ml of water and 10 ml of methanol. However, the mixture must at the end still retain an acidic pH. The sodium sulfate is filtered off and the filtrate is fully concentrated under vacuum.
- compositions of three adhesion promoters according to the invention are shown in the following table (examples 1-3)
- Example 1 Example 2
- Example 3 Phosphonate 10 g 1 g 1 g formula (7) formula (9) formula (10) H 2 O 5 g 1 g 1.5 g Ethanol 20 g 4.5 g 10 g Bis-GMA* 25 g 0.75 g 1 g TEDMA** 25 g 1.25 g 5 g HEMA*** 15 g 1.5 g 1.5 g Ethyl dimethyl- 0.15 g 0.018 g 0.018 g aminobenzoate Camphorquinone 0.1 g 0.014 g 0.014 g *2,2-Bis-[4-(2-hydroxy-3-methacryloyloxypropyl)phenyl]propane **Triethylene glycol dimethacrylate ***2-Hydroxyethyl methacrylate
- composition of an adhesion promoter system consisting of a primer, which as active substance comprises one of the adhesion monomers according to the invention, and a bond, which in a second step is applied to a dental hard substance, provided beforehand with primer, is compiled below:
- the individual substances of the primer are weighed out in a glass vessel and are mixed at ambient temperature with stirring until a homogeneous solution is produced.
- composition of an adhesion promoter system consisting of a component which comprises, inter alia, one of the adhesion monomers according to the invention, is compiled in the table below.
- the individual substances of the adhesion promoter are weighed out in each case in a glass vessel and are mixed at ambient temperature with stirring until a homogeneous solution is produced.
- a shear bond test is carried out to measure the adhesion of composites to dental hard substance when using the adhesion promoters according to the invention.
- cattle incisors from which the pulp has been removed beforehand and which in addition have been stored in 0.5% by weight chloramine T solution in water, are ground down under wet conditions on the front down to the dentin and are subsequently sanded flat under wet conditions with a fine sandpaper (P500). After storing for a short time in demineralized water, the sanded surface is blown dry and the adhesion promoter system is applied.
- the primer from example 4 is rubbed into the sanded dentin surface with a microbrush for 20 s. Subsequently, the bond from example 4 is analogously applied, the surface is blown and is exposed to a dental lamp (Translux EC, Fa. Kulzer & Co GmbH, Wehrheim, Germany) for 20 s.
- a dental lamp Translux EC, Fa. Kulzer & Co GmbH, Wehrheim, Germany
- a two-part Teflon mold with a cavity with a diameter of 3.0 mm is assembled, filled with a dental composite (Ecusit, Dental Material Weg mbH, Hamburg, Germany) and exposed for 40 s (Kulzer Translux EC).
- the adhesion promoter from example 5 is rubbed into the sanded dentin surface with a microbrush for 20 s. Subsequently, the surface is blown and exposed to a dental lamp (Translux EC, Fa. Kulzer & Co GmbH, Wehrheim, Germany) for 20 s. The adhesion promoter from example 5 is again rubbed into the dentin surface with a microbrush for 20 s, the surface is blown and exposed to a dental lamp (Translux EC, Fa. Kulzer & Co GmbH, Wehrheim, Germany) for 20 s.
- a two-part Teflon mold with a cavity with a diameter of 3.0 mm is assembled, filled with a dental composite (Ecusit, Dental Material Weg mbH, Hamburg, Germany) and exposed for 40 s (Kulzer Translux EC).
- the bond from example 6 is rubbed into the sanded dentin surface with a microbrush for 20 s, blown with compressed air and exposed to a dental lamp (Translux EC, Fa. Kulzer & Co GmbH, Wehrheim, Germany) for 20 s.
- a dental lamp Translux EC, Fa. Kulzer & Co GmbH, Wehrheim, Germany
- a two-part Teflon mold with a cavity with a diameter of 3.0 mm is assembled, filled with a dental composite (Ecusit, Dental Material Weg mbH, Hamburg, Germany) and exposed for 40 s (Kulzer Translux EC).
- the Teflon mold is in each case removed and the preparation is stored in water, first at 37° C. for 23 h and then at 23° C. for 1 h.
- the preparation is subsequently inserted into a mounting for measurement of the shear bond strength (see ISO/DTS Committee Draft 11405, Ref. No. ISO/TC 106/SC 1 N 321 and the literature cited therein) and measured in an apparatus for determination of a force-displacement diagram (Z010, Zwick GmbH & Co, Ulm, Germany) at an advance rate of 0.50 mm/min.
- the test is carried out on several preparations (number n).
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- Organic Chemistry (AREA)
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Abstract
Description
in which R, R7 and p are, independently of one another:
either:
-
- a) R: alkyl group or alkylene group with at least 6 C-atoms or aryl group,
- R7: H, methyl, ethyl, propyl, isopropyl or butyl,
- p is 1 or 2;
- or:
- b) R: —CO—NR1—R8—
- with R1 equal to H, alkyl or aryl,
- with R8 equal to aryl or CnH2n
- in which 4≦n≦18,
- or R8 is CnH2n—Si(R5)2—[O—Si(R5)2]m—CnH2n
- in which 3≦n≦12,
- 1≦m≦10, and
- R5 is methyl, ethyl or phenyl,
- or R8 is CnH2n—COONH—CnH2n
- in which 4≦n≦12, and in which R8 can have ether or additional urethane groups,
- R7 and p are defined as in a);
- or:
- c) R:
- with R10 chosen from the group consisting of aryl groups, alkyl groups with at least 3 C-atoms or polyether groups with 1 to 10 polyether units and with R11 chosen, identically or differently, from the group consisting of alkyl groups and aryl groups,
- with X equal to N, B or CH,
- R7: COOR9, CONHR9, H or phenyl with R9 chosen from the group consisting of methyl, ethyl, propyl, isopropyl and butyl,
- p is equal to 2.
- a) R: alkyl group or alkylene group with at least 6 C-atoms or aryl group,
R1 is hydrogen or an alkyl or aryl group. Preferably, R1 is chosen from the group consisting of hydrogen, methyl, ethyl and isopropyl. R2 is an alkyl group with 4 to 18 C-atoms which can be straight or branched. Preferably, it comprises 6 to 12 C-atoms. In the context of the invention, R2 can also have the form of an alkyl chain interrupted by ether groups or additional urethane groups.
-
- 2.5 to 60% by weight of phosphonic acids according to the invention or of their salts,
- 5 to 80% by weight of additional radically polymerizable comonomers,
- 0 to 80% by weight of solvents,
- 0 to 2% by weight of radical polymerization initiators,
- 0 to 80% by weight of fillers (depending on the intended application as adhesion promoter, cement or compomer).
Example 1 | Example 2 | Example 3 | ||
Phosphonate | 10 g | 1 g | 1 g | ||
formula (7) | formula (9) | formula (10) | |||
H2O | 5 g | 1 g | 1.5 g | ||
Ethanol | 20 g | 4.5 g | 10 g | ||
Bis-GMA* | 25 g | 0.75 g | 1 g | ||
TEDMA** | 25 g | 1.25 g | 5 g | ||
HEMA*** | 15 g | 1.5 g | 1.5 g | ||
Ethyl dimethyl- | 0.15 g | 0.018 g | 0.018 g | ||
aminobenzoate | |||||
Camphorquinone | 0.1 g | 0.014 g | 0.014 g | ||
*2,2-Bis-[4-(2-hydroxy-3-methacryloyloxypropyl)phenyl]propane | |||||
**Triethylene glycol dimethacrylate | |||||
***2-Hydroxyethyl methacrylate |
Substance | Proportion/% by weight |
4-Methacrylamido-4-methylpentyl- | 40.000 |
phosphonic acid (formula (9)) | |
Water | 28.875 |
Ethanol | 28.875 |
Camphorquinone | 0.800 |
2-Ethylhexyl 4-(dimethylamino)benzoate | 1.400 |
2,6-Di(tert-butyl)-4-methylphenol | 0.050 |
Substance | Proportion/% by weight |
4-Methacrylamido-4-methylpentyl- | 10.00 |
phosphonic acid (formula (9)) | |
Water | 10.00 |
Ethanol | 44.28 |
Glycerin-1,3-dimethacrylate | 10.97 |
Hydroxyethyl methacrylate | 15.00 |
Bis-GMA | 7.50 |
Camphorquinone | 0.80 |
2-Ethylhexyl 4-(dimethylamino)benzoate | 1.40 |
2,6-Di(tert-butyl)-4-methylphenol | 0.05 |
Shear bond strength | ||
Mean value | ||
Example | n | [MPa] |
4 | 10 | 17 |
5 | 3 | 9 |
6 | 10 | 01) |
1)Composite test specimens become detached without resistance from the dentin surface. |
Claims (13)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP00114527A EP1169996A1 (en) | 2000-07-06 | 2000-07-06 | Phosphonic acid containing dental material |
EP001145275 | 2000-07-06 | ||
PCT/EP2001/007602 WO2002002057A1 (en) | 2000-07-06 | 2001-07-03 | Dental material containing phosphonic acids |
Publications (2)
Publication Number | Publication Date |
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US20030167968A1 US20030167968A1 (en) | 2003-09-11 |
US6902608B2 true US6902608B2 (en) | 2005-06-07 |
Family
ID=8169179
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US10/332,344 Expired - Lifetime US6902608B2 (en) | 2000-07-06 | 2001-07-03 | Dental material containing phosphonic acids |
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US (1) | US6902608B2 (en) |
EP (2) | EP1169996A1 (en) |
JP (2) | JP5128748B2 (en) |
DE (1) | DE50107506D1 (en) |
WO (1) | WO2002002057A1 (en) |
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US20040156795A1 (en) * | 2001-07-09 | 2004-08-12 | Kimiya Nemoto | Dental self-etching primer |
US20060142515A1 (en) * | 2002-09-11 | 2006-06-29 | Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung E.V. | Carboxylic acid derivatives containing phosphorous groups and organically polymerisable groups |
WO2011050534A1 (en) * | 2009-10-30 | 2011-05-05 | Rhodia (China) Co., Ltd. | N-substituted acrylamides, preparation method and use thereof |
WO2011050537A1 (en) * | 2009-10-30 | 2011-05-05 | Rhodia (China) Co., Ltd. | Conjugated diene phosphinate compounds, preparation method and use thereof |
US20110250557A1 (en) * | 2007-10-08 | 2011-10-13 | Kerr Corporation | Dental adhesive and method of use |
US9783559B2 (en) | 2013-06-20 | 2017-10-10 | Ivoclar Vivadent Ag | β-Ketophosphonic acids and dental materials based thereon |
US9833389B2 (en) | 2015-07-22 | 2017-12-05 | Ivoclar Vivadent Ag | Adhesive dental materials with strongly acidic adhesive polymers |
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US20040266906A1 (en) * | 2001-10-26 | 2004-12-30 | Joachim Klee | Hydrolysis stable self-etching,self-priming adhesive |
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US7777080B2 (en) * | 2002-09-11 | 2010-08-17 | Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung E.V. | Carboxylic acid derivatives containing phosphorous groups and organically polymerizable groups |
US8297976B2 (en) * | 2007-10-08 | 2012-10-30 | Kerr Corporation | Dental adhesive and method of use |
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WO2011050537A1 (en) * | 2009-10-30 | 2011-05-05 | Rhodia (China) Co., Ltd. | Conjugated diene phosphinate compounds, preparation method and use thereof |
CN102596976A (en) * | 2009-10-30 | 2012-07-18 | 罗地亚(中国)投资有限公司 | N-substituted acrylamides, preparation method and use thereof |
CN102596974A (en) * | 2009-10-30 | 2012-07-18 | 罗地亚(中国)投资有限公司 | Conjugated diene phosphinate compounds, preparation method and use thereof |
WO2011050534A1 (en) * | 2009-10-30 | 2011-05-05 | Rhodia (China) Co., Ltd. | N-substituted acrylamides, preparation method and use thereof |
US8835674B2 (en) | 2009-10-30 | 2014-09-16 | Solvay (China) Co., Ltd. | Conjugated diene phosphinate compounds, preparation method and use thereof |
US9120917B2 (en) | 2009-10-30 | 2015-09-01 | Solvay China Co., Ltd. | N-substituted acrylamides, preparation method and use thereof |
CN102596976B (en) * | 2009-10-30 | 2015-11-25 | 罗地亚(中国)投资有限公司 | Acrylamide, Preparation Method And The Use that N-replaces |
US9783559B2 (en) | 2013-06-20 | 2017-10-10 | Ivoclar Vivadent Ag | β-Ketophosphonic acids and dental materials based thereon |
US9833389B2 (en) | 2015-07-22 | 2017-12-05 | Ivoclar Vivadent Ag | Adhesive dental materials with strongly acidic adhesive polymers |
US10188588B2 (en) * | 2016-03-31 | 2019-01-29 | Ivoclar Vivadent Ag | Acidic hybrid monomers and dental materials based thereon |
Also Published As
Publication number | Publication date |
---|---|
EP1169996A1 (en) | 2002-01-09 |
JP5681848B2 (en) | 2015-03-11 |
EP1296634A1 (en) | 2003-04-02 |
US20030167968A1 (en) | 2003-09-11 |
JP2004501940A (en) | 2004-01-22 |
EP1296634B1 (en) | 2005-09-21 |
JP5128748B2 (en) | 2013-01-23 |
JP2013010784A (en) | 2013-01-17 |
WO2002002057A1 (en) | 2002-01-10 |
DE50107506D1 (en) | 2006-02-02 |
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